CN105161555B - Single-crystal particle film and preparation method of substrate-free flexible solar cell employing single-crystal particle film - Google Patents
Single-crystal particle film and preparation method of substrate-free flexible solar cell employing single-crystal particle film Download PDFInfo
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- CN105161555B CN105161555B CN201510509635.9A CN201510509635A CN105161555B CN 105161555 B CN105161555 B CN 105161555B CN 201510509635 A CN201510509635 A CN 201510509635A CN 105161555 B CN105161555 B CN 105161555B
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- 239000013078 crystal Substances 0.000 title claims abstract description 157
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000002245 particle Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000010409 thin film Substances 0.000 claims description 75
- 239000003822 epoxy resin Substances 0.000 claims description 38
- 229920000647 polyepoxide Polymers 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 30
- 239000010408 film Substances 0.000 claims description 26
- 239000000853 adhesive Substances 0.000 claims description 22
- 230000001070 adhesive effect Effects 0.000 claims description 22
- 239000002270 dispersing agent Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000002105 nanoparticle Substances 0.000 claims description 20
- 239000010453 quartz Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
- 230000004907 flux Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000004544 sputter deposition Methods 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 210000001142 back Anatomy 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052756 noble gas Inorganic materials 0.000 claims description 4
- 150000002835 noble gases Chemical class 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- 239000004945 silicone rubber Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- NKSXAYFZXLTLDA-UHFFFAOYSA-N [S].[Se].[Sn].[Zn] Chemical compound [S].[Se].[Sn].[Zn] NKSXAYFZXLTLDA-UHFFFAOYSA-N 0.000 claims 1
- 238000004026 adhesive bonding Methods 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 60
- 238000004140 cleaning Methods 0.000 abstract description 9
- 238000001020 plasma etching Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 3
- 239000002346 layers by function Substances 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 229920000620 organic polymer Polymers 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229920000084 Gum arabic Polymers 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000205 acacia gum Substances 0.000 description 4
- 235000010489 acacia gum Nutrition 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000005253 cladding Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- -1 Sodium dialkyl sulfate Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229950007687 macrogol ester Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/0242—Crystalline insulating materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a single-crystal particle film and a preparation method of a substrate-free flexible solar cell employing the single-crystal particle film. With an organic polymer material as a binder, micron-sized CZTS and CZTSSe single-crystal particles are mixed into the binder; the single-crystal particle film is prepared by a coating method; the single-crystal particles leaking from the binder on two surfaces are removed through mechanical grinding and plasma etching; and functional layers such as a buffer layer, a window layer and an electrode are prepared, so as to form an entire battery structure. Preparing, screening, cleaning and passivating processes of the single-crystal particles and the preparation process of a single-crystal particle absorption layer are separate, and a harsh high-temperature environment can be used in the preparation and optimization processes of the single-crystal particles, so that effective control on components of CZTS and CZTSSe is achieved; the effects to a substrate, the window layer, the buffer layer and the like caused by preparation conditions of the absorption layer do not need to be considered; and the method has significant advantages in the aspects of material and energy utilization rate and industrial production.
Description
Technical field
The present invention relates to photoelectric semiconductor material and device arts, more particularly, to a kind of single crystal grain thin film
And its preparation method of linerless bottom flexible solar battery.
Background technology
Copper-zinc-tin-sulfur (czts) quaternary compound and copper zinc tin sulfur selenium (cztsse) quasiconductor are considered as to be hopeful most to take
For CIGS cu (in, ga) se2The new compound quasiconductor of absorbing layer of thin film solar cell.First, from crystal structure
On from the point of view of, custerite type czts be by zn and sn replace Chalkopyrite phase cuin2Two in s develop, therefore,
The preparation method of cigs and battery structure are generally applicable for czts.Czts and cztsse is also direct band gap p-type semiconductor, light
Big (> 10 of absorptance4Cm), its energy gap is 1.5 ev, cu2znsns4Bandwidth adjustable between 1.5 ev and 1.0 ev,
Close to unijunction solar cell optimum band gap 1.4ev it means that they as absorbed layer make battery be likely to be breached very high
Conversion efficiency；Importantly, the component of czts rich reserves in the earth's crust, substantially nontoxic.Above-mentioned advantage makes
Czts becomes replacement cigs thin film, green, the optimal candidate material of solar battery obsorbing layer that is cheap, being suitable for large-scale production
Material.
Compared with binary and ternary semiconductor, this based semiconductor of czts and cztsse, due to the increase of component, leads to
It has more complicated physical property so that the preparation of high efficiency hull cell and performance optimization become more difficult；Simultaneously
The Thermodynamically stable region of czts and cztsse phase is very little, and various impurities phases, metastable phase and czts vie each other, and therefore exist
In czts and cztsse membrane-film preparation process, easily with various binary, ternary dephasign and some metastable phases occur, finally right
Czts and cztsse battery performance brings adverse effect, this to the component controllable standby of czts and cztsse be one very big
Challenge.If being not carried out effective component in czts and cztsse membrane-film preparation process to control, due to Partial Elements volatilization,
Lead to nonstoichiometry ratio, then dephasign occurs.So, first prepare monocrystal material, recycle single crystal grain film technique
Preparing battery becomes the effective way solving these problems.
Content of the invention
The purpose of the present invention is to overcome component in czts and cztsse membrane-film preparation process in prior art to be difficult to
Effect controls, and the defects such as metastable phase, dephasign easily, provides a kind of preparation method of single crystal grain thin film.
Second object of the present invention is to provide said method to prepare linerless bottom flexible unitary particle film.
Third object of the present invention is to provide to contain above-mentioned linerless bottom flexible unitary particle film solaode.
Fourth object of the present invention is the preparation method providing above-mentioned solaode.
The purpose of the present invention is achieved by the following technical programs:
A kind of preparation method of single crystal grain thin film, comprises the following steps:
S1. using czochralski method, one layer of Radix Acaciae senegalis thin film is prepared on substrate；
S2. choose 75～97 μm of single crystal grain, and mix with adhesive, add dispersant afterwards；Described single crystal grain
Volume ratio with adhesive is 1:1.5～2, and the addition of described dispersant is single crystal grain and adhesive mixture quality summation
0.1～1%；
S3. the mixture of single crystal grain, adhesive and dispersant is coated on Radix Acaciae senegalis thin film, cured, grind
After mill exposes single crystal grain surface, cleaning-drying obtains final product single crystal grain thin film；
Adhesive described in s2 is selected from epoxy resin, polyurethane adhesive, silicone rubber.
The preparation of existing thin-film solar cells and thin film is simultaneously, and the preparation of such film absorption layer then can affect too
Sun can battery performance, the single crystal grain that the present invention prepares by using solvent-thermal method is as the main one-tenth of film absorption layer
Point, with the adhesives such as epoxy resin, polyurethane adhesive, silicone rubber and dispersant, prepare the single crystal grain thin film of function admirable
Absorbed layer, when preparing single crystal grain, selects the seed crystal adding nanometer copper-zinc-tin-sulfur nano-particle to grow as single crystal grain, with
When reaction raw materials, flux and seed crystal are ground, obtain pattern rule, the homogeneous presoma of component, this presoma existed
Certain temperature and reaction under the response time, you can prepare morphology controllable, the controlled single crystal grain of component；Due to single crystal grain
Use, each single crystal grain forms a battery unit, it is possible to achieve the component of effective control copper-zinc-tin-sulfur and copper zinc tin sulfur selenium,
The impact to device performance for the defect and interface impurity of reduction film absorption layer, this thin film can be used for subsequently preparing thin film solar
Battery.
Inventor is found by research, in fact, being difficult to prepare conjunction just with single crystal grain and adhesive, dispersant
Suitable single crystal grain thin film is it is necessary to strictly control single crystal grain and adhesive, the selection of dispersant and proportioning, after inventor's research
Find only have the ratio of single crystal grain, adhesive and dispersant just can successfully obtain single crystal grain within the above range.
Preferably, described dispersant be aqueous wetting agent dispersant, it is highly preferred that described dispersant be polyacrylamide, ten
Sodium dialkyl sulfate, fatty acid polyethylene glycol ester.
Preferably, the amount of described single crystal grain is 10～20g.
Preferably, the thickness of the Radix Acaciae senegalis thin film described in s1 is 20～40 μm.
Preferably, the coating thickness of the mixture of single crystal grain, adhesive and dispersant described in s3 is 110～130 μm.
Preferably, the grinding described in s3 refers to grind away Radix Acaciae senegalis thin film and adhesive, and the thickness of grinding is 70～
90μm.
Preferably, the cleaning described in s3 is using hcl and deionized water cleaning.
Preferably, single crystal grain described in s2 in said method be with elemental copper, zinc, stannum, sulfur powder/metal sulfide or
Elemental copper, zinc, stannum, sulfur, selenium powder/metal sulfide are source material, add flux potassium iodide or cesium chloride, with appropriate copper
Zinc-tin sulfur nano-particle is sufficiently mixed grinding, then puts into the copper-zinc-tin-sulfur preparing micron level in quartzy bottle with molten-salt growth method
Or copper zinc tin sulfur selenium single crystal grain.
Preferably, described single crystal grain is copper-zinc-tin-sulfur single crystal grain or copper zinc tin sulfur selenium single crystal grain, wherein, described
The preparation method of copper-zinc-tin-sulfur single crystal grain is: (1) is by reaction raw materials elemental copper powder/cus powder, simple substance zinc powder/zns powder
End, simple substance tin powder/sns powder, simple substance sulfur powder or cus powder, zns powder, the mixing of sns powder, add flux, copper zinc
Stannum sulfur nano-particle ground and mixed is uniformly configured to presoma；Copper in described reaction raw materials, zinc, stannum, four kinds of elements of sulfur mole
Than for cu/ (zn+sn)=0.76～0.95, zn/sn=1.1～1.2, (cu+zn+sn)/s=1；(2) presoma is loaded quartz
In reaction vessel, evacuation or seal quartz reaction container using high temperature oxyhydrogen flame after being passed through noble gases；(3) by after sealing
Quartz reaction container keeps 48～120h at 750～1000 DEG C, to quartz reaction container fast cooling to room temperature, takes out quartz
Sample in reaction vessel, obtains final product copper-zinc-tin-sulfur single crystal grain after washing, drying；
The preparation method of described copper zinc tin sulfur selenium single crystal grain is: (1) is by reaction raw materials elemental copper powder/cus powder, list
Matter zinc powder/zns powder, simple substance tin powder/sns powder, simple substance sulfur powder, simple substance selenium powder or cus powder, zns powder,
Sns powder, the mixing of se powder, add flux, copper-zinc-tin-sulfur nano-particle ground and mixed to be uniformly configured to presoma；Described anti-
Copper in raw material, zinc, stannum, sulfur, the mol ratio of five kinds of elements of selenium is answered to be: cu/ (zn+sn)=0.76～0.95, zn/sn=1.1～
1.2, (cu+zn+sn)/(s+se)=0.8～1, se/s=0.1～0.9；(2) presoma is loaded in quartz reaction container by s2.,
Evacuation or seal quartz reaction container after being passed through noble gases；(3) s3. by the quartz reaction container after sealing 750～
Keep 48～120h at 1000 DEG C, to quartz reaction container fast cooling to room temperature, take out the sample in quartz reaction container, wash
Wash, be dried after obtain final product copper zinc tin sulfur selenium single crystal grain；
The preparation method of described copper-zinc-tin-sulfur nano-particle is: (1) is by zinc chloride, stannous chloride, copper chloride by 1:1:2's
Mol ratio is soluble in water to stir to obtain settled solution a；(2) solution b is the thiourea solution of 0.1～0.3m, described solution a and solution b
Volume ratio be 2.5～3.5:1.5～2.5, solution b is added slowly in solution a under agitation, obtains turbid solution, it
After be stirred for obtaining mixed solution；(3) mixed solution is placed in 170～190 DEG C of reaction 15～18h in autoclave, is cooled to
Copper-zinc-tin-sulfur nano-particle is obtained after washing, be centrifuged, being dried after room temperature.
The single crystal grain thin film that any of the above-described kind of method prepares is provided.
As a kind of preferred embodiment, the preparation method of single crystal grain thin film of the present invention comprises the following steps:
S1. using czochralski method, one layer of Radix Acaciae senegalis thin film is prepared on the glass substrate cleaning up；
S2. weigh 75～97 μm of czts or cztsse single crystal grain, above-mentioned granule is evenly mixed in epoxy resin
In, described single crystal grain is 1:2 with the volume ratio of epoxy resin, and adds single crystal grain and epoxy resin composition quality summation
0.1～1% dispersant (polyacrylamide, sodium lauryl sulphate or fatty acid polyethylene glycol ester)；
S3. the epoxy resin being mixed with single crystal grain is coated on Radix Acaciae senegalis thin film, after solidification, grinds away table
The epoxy resin of layer, exposes single crystal grain, cleaned, be drying to obtain single crystal grain thin film.
The present invention also provides the linerless bottom flexible unitary particle film solaode containing above-mentioned single crystal grain thin film, tool
Body ground, the preparation method of described solaode is as follows:
S1. using the molybdenum film of 1～2 μm of single crystal grain film surface sputtering sedimentation as dorsum electrode layer；
S2. take out sample, separate single crystal grain thin film and dry, single crystal grain thin film is laid in hard substrates (for example
Glass) on, it is coated with the surface of mo thin film down, etch away Radix Acaciae senegalis and the epoxy resin of single crystal grain remained on surface；
S3., cds cushion, Window layer i-zno and transparent electrode layer azo are sequentially prepared on single crystal grain thin film, evaporation
Electrode, encapsulation, obtain final product linerless bottom flexible unitary granule solaode.
Preferably, the thickness of described cds cushion is 40～60nm；Described Window layer i-zno and transparent electrode layer azo's
Thickness is respectively 100～400nm and 0.4～1 μm；Etch period described in s2 is 5～15min.
As a kind of preferred embodiment, prepared by linerless bottom of the present invention flexible unitary particle film solaode
Method comprises the following steps:
S1. using czochralski method, one layer of Radix Acaciae senegalis thin film is prepared on the glass substrate cleaning up；
S2. weigh 75～97 μm of czts or cztsse single crystal grain, above-mentioned granule is evenly mixed in epoxy resin
In, described single crystal grain is 1:2 with the volume ratio of epoxy resin, and adds brilliant granule and epoxy resin composition quality summation
0.1～1% dispersant (polyacrylamide, sodium lauryl sulphate or fatty acid polyethylene glycol ester)；
S3. the epoxy resin being mixed with single crystal grain is coated on Radix Acaciae senegalis thin film, after solidification, grinds away table
Layer epoxy resin, expose single crystal grain, cleaned, be dried after, send into sputtering chamber sputter one layer of molybdenum film；
S4. take out sample, soak in deionized water and take thin film off after separating substrate and acacia gum layer and dry,
Then thin film is laid on glass, is coated with the surface of mo thin film down, send into plasma etching room, etch away particle surface
The Radix Acaciae senegalis of residual and epoxy resin, expose the spherical surface of single crystal grain；
S5. utilize cbd method to prepare cds cushion on surface, be re-fed into sputtering chamber and Window layer is prepared on cds cushion
Zinc oxide (i-zno) and transparent electrode layer Al-Doped ZnO (azo), last electrode evaporation, form complete battery.
Compared with prior art, the method have the advantages that
The invention provides a kind of preparation method of single crystal grain thin film, that is, using high-molecular organic material as binding agent,
Czts the and cztsse single crystal grain of micron level is blended in macromolecular material, prepares the monocrystalline of monolayer using cladding process
Grain thin film, spills single crystal grain, preparation buffering by the binding agent that mechanical lapping and plasma etching remove two sides afterwards again
The functional layers such as layer, Window layer, electrode are thus form complete battery structure.Due to the preparation of single crystal grain, screening, cleaning, blunt
The preparation process of change process and single crystal grain absorption tunic is separate, can use in single crystal grain preparation and optimization process
Harsh hot environment, thus realizing the component of czts or cztsse is effectively controlled, and need not consider absorbed layer system
Standby conditions on substrate, the impact of Window layer, cushion etc., the method has in terms of material with energy utilization rate and industrialized production
There is obvious advantage.
Brief description
Fig. 1 is the preparation process of solar film battery of the present invention；Wherein, fig. 1 is on common glass substrate
Prepare Radix Acaciae senegalis；Fig. 2 is the asphalt mixtures modified by epoxy resin that coating is mixed with czts or cztsse single crystal grain on Radix Acaciae senegalis
Fat；Fig. 3 is to grind away one layer of epoxy resin to make czts or cztsse single crystal grain surface exposure；Fig. 4 is to use sputtering method
Prepare mo dorsum electrode layer on the surface exposing czts or cztsse single crystal grain；Fig. 5 is to soak in deionized water to separate
Take thin film off after substrate and acacia gum layer and dry, be coated with mo thin film one is placed face down in support substrate.
Fig. 2 is the preparation process of solar film battery of the present invention；Wherein, fig. 6 is with plasma etching
The Radix Acaciae senegalis of grain remained on surface and epoxy resin make thin film expose the spherical surface of czts or cztsse single crystal grain；fig.
7 is to prepare cds cushion with cbd method in the spherical surface of czts or cztsse single crystal grain；Fig. 8 is in cds with sputtering method
I-zno Window layer is prepared on cushion；Fig. 9 is to prepare azo transparent electrode layer in i-zno Window layer with sputtering method；fig.
10 is electrode evaporation, encapsulation, and preparation completes flexible linerless bottom czts or cztsse single crystal grain solaode.
Description of reference numerals: 11- single crystal grain；12-cds cushion；13-i-zno Window layer；14-azo transparency electrode
Layer；15-mo thin film；21- epoxy resin；22- Radix Acaciae senegalis thin film；31- glass；32- glass substrate；41- encapsulating material
eva.
Specific embodiment
Further illustrate present disclosure with reference to Figure of description and specific embodiment, but should not be construed as to this
The restriction of invention.Without departing from the spirit and substance of the case in the present invention, that the inventive method, step or condition are made is simple
Modification or replacement, belong to the scope of the present invention；If not specializing, in embodiment, technological means used are art technology
Conventional meanses known to personnel.
Embodiment 1
The present embodiment is to prepare solaode using czts single crystal grain, comprises the following steps:
(1) preparation of czts single crystal grain:
1st, hydro-thermal method preparation cu2znsns4Nano-particle: by 2 mmol cucl2·2h2o、1 mmol zncl2、1 mmol
sncl4·5h2O is dissolved in 30ml deionized water, and stirring 10min obtains settled solution a；5 mmol thiourea are dissolved in 20ml deionized water
In, stirring 10min obtains settled solution b；Solution b is added slowly in solution a under agitation, obtains white opacity solution, stir
Mix 10 min and obtain mixed solution, be placed in 180 DEG C by mixed solution immigration 100ml politef autoclave and by reactor
Reaction 16h, is cooled to room temperature deionized water and dehydrated alcohol centrifugation under the conditions of 8000r/min respectively, 60 DEG C of dryings
8h obtains black sample, i.e. czts nano-particle.
2nd, molten-salt growth method preparation cu2znsns4Micron single crystal grain: weigh reaction raw materials 18 mmol cus, 12 mmol zns,
10 mmol sns and flux 50 mmol cscl, and add 1 mmol czts nano-particle to be fully ground after mixing, make
Its mix homogeneously；Mixed sample is loaded in quartzy bottle, reach 10 by three-way valve using vacuum pump assembly evacuation～
102Pa(can also blanketing with inert gas), thus excluding the impact that air reacts to fused salt, with oxyhydrogen flame, quartzy bottle is sealed
Mouthful；Quartzy bottle equipped with biased sample after sealing is placed in common heating furnace and is heated to 800 DEG C of holding 72h from room temperature, then
Cool to 600 DEG C and take out quartzy bottles and fast cooling is to room temperature (putting in water)；Finally the sample in quartzy bottle is taken out, ultrasonic
Washing repeatedly removes flux cscl, afterwards sample is placed in 80 DEG C of drying 2 h of drying baker, obtains surface and have crystal gloss
Black particle, finally the sample of gained is sieved (test sieve each layer aperture is 97 μm from top to bottom successively, 75 μm, 57 μm,
49 μm) obtain the micron-scale single crystal grain wanted.
(2) preparation of single crystal grain solaode:
1st, preparing a layer thickness in the glass substrate cleaning up using czochralski method is 30 μm of Radix Acaciae senegalis thin film.
2nd, weigh the czts single crystal grain 10g using molten-salt growth method preparation, sieved (test sieve each layer hole using test sieve
Footpath is 97 μm from top to bottom successively, 75 μm, 57 μm, 49 μm), choose 75～97 μm of granule.
3rd, above-mentioned granule is evenly mixed in epoxy resin (or polyurethane adhesive, silicone rubber), single crystal grain and epoxy
The volume ratio of resin is 1:2, and add single crystal grain and epoxy resin quality summation 0.1% polyacrylamide amine dispersant (or
Person's sodium lauryl sulphate, fatty acid polyethylene glycol ester), then, coat one layer using cladding process on Radix Acaciae senegalis thin film
Thickness is 120 μm of the epoxy resin being mixed with czts single crystal grain.
4th, after epoxy resin cure, grind away the epoxy resin on 80 μm of top layer using grinder, expose czts monocrystalline
Grain.
5th, clean up, using hcl and deionized water, the surface exposing czts single crystal grain, dry.
6th, thin film is sent into sputtering chamber, 2 μm of surface sputtering sedimentation exposing czts single crystal grain mo thin film as the back of the body
Electrode layer.
7th, take out sample, soak in deionized water and take thin film off after separating substrate and acacia gum layer, dry.
8th, the thin film taken off is laid on glass, is coated with the surface of mo layer down, send into plasma etching room, utilize
Plasma etching 10min, etches away Radix Acaciae senegalis and the epoxy resin of particle surface residual, exposes czts or cztsse mono-
The spherical surface of brilliant granule.
The 9th, the cds cushion of 50nm is prepared using cbd method on czts single crystal grain spherical surface.
10th, the thin film being prepared for cds cushion is sent into sputtering chamber, preparation is successively sputtered on cds cushion and is about
The azo thin film of the i-zno layer of 200nm and 1 μm.
11st, take down support substrate, electrode evaporation, form complete no substrate flexibility czts single crystal grain solaode.
The film preparation solaode of the mo/czts/cds/i-zno/azo structure that the present embodiment prepares, it is opened
Road voltage voc=440mv, i=20ma, ff=46%, the conversion ratio of battery is 5.8%.
Embodiment 2
Experimental technique with embodiment 1, unique unlike czts single crystal grain preparation, comprise the following steps:
1st, hydro-thermal method preparation cu2znsns4Nano-particle: with embodiment 1.
2nd, reaction raw materials 18 mmol cus, 12 mmol zns, 10 mmol sn powder, 10mmol s powder and flux are weighed
50 mmol cscl, and it is fully ground so as to mix homogeneously after adding 1 mmol czts nano-particle mixing；To grind all
Biased sample after even loads in quartzy bottle, reaches 10～10 by three-way valve using vacuum pump assembly evacuation2Pa(can also
Blanketing with inert gas), thus excluding the impact that air reacts to fused salt, with oxyhydrogen flame by quartzy bottle closure；To fill after sealing
The quartzy bottle having biased sample is placed in common heating furnace and is heated to 850 DEG C of holding 72h from room temperature, then cools to 600 DEG C of left sides
Right take out quartzy bottle and fast cooling is to room temperature (putting in water)；Finally the sample in quartzy bottle is taken out, ultrasonic washing is repeatedly
Remove flux cscl, afterwards sample is placed in 80 DEG C of drying 2 h of drying baker, obtains the black that surface has crystal gloss
Grain.Finally the sample of gained is sieved (test sieve each layer aperture is 97 μm, 75 μm, 57 μm, 49 μm from top to bottom successively)
Obtain the micron-scale single crystal grain wanted.
Embodiment 3
Experimental technique with embodiment 1, unique unlike czts single crystal grain preparation, comprise the following steps:
1st, hydro-thermal method preparation cu2znsns4Nano-particle: with embodiment 1.
2nd, reaction raw materials 18 mmol cu, 12 mmol zn, 10 mmol sn powder, 40 mmol s powder and flux are weighed
80 mmol cscl, and it is fully ground so as to mix homogeneously after adding 2 mmol czts nano-particle mixing；To grind all
Biased sample after even loads in quartzy bottle, reaches 10～10 by three-way valve using vacuum pump assembly evacuation2Pa(can also
Blanketing with inert gas), thus excluding the impact that air reacts to fused salt, with oxyhydrogen flame by quartzy bottle closure；To fill after sealing
The quartzy bottle having biased sample is placed in common heating furnace and is heated to 850 DEG C of holding 72h from room temperature, then cools to 600 DEG C of left sides
Right take out quartzy bottle and fast cooling is to room temperature (putting in water)；Finally the sample in quartzy bottle is taken out, ultrasonic washing is repeatedly
Remove flux cscl, afterwards sample is placed in 80 DEG C of drying 2 h of drying baker, obtains the black that surface has crystal gloss
Grain.Finally the sample of gained is sieved (test sieve each layer aperture is 97 μm, 75 μm, 57 μm, 49 μm from top to bottom successively)
Obtain the micron-scale single crystal grain wanted.
Embodiment 4
The present embodiment is to prepare solaode using cztsse single crystal grain, comprises the following steps:
(1) preparation of cztse single crystal grain:
1st, hydro-thermal method preparation cu2znsns4Nano-particle: with embodiment 1.
2nd, 18 mmol cus, 12 mmol zns, 10 mmol sns, 10mmol se, 30 mmol cscl and 20 are weighed
Mmol ki, and it is fully ground so as to mix homogeneously after adding 1 mmol czts nano-particle mixing；After grinding uniformly
Biased sample loads in quartzy bottle, reaches 10～10 by three-way valve using vacuum pump assembly evacuation2Pa(can also use inertia
Gas shield), thus excluding the impact that air reacts to fused salt, with oxyhydrogen flame by quartzy bottle closure；Equipped with mixing after sealing
The quartzy bottle of sample is placed in common heating furnace and is heated to 800 DEG C of holding 60h from room temperature, then cools to 600 DEG C about taking-ups
Quartzy bottle fast cooling are to room temperature (putting in water)；Sample is taken out from quartzy bottle, ultrasonic washing repeatedly removes flux
Cscl and ki, sample is placed in 80 DEG C of drying 2 h of drying baker, obtains the black particle that surface has crystal gloss.Finally by institute
Sample sieved that (test sieve each layer aperture is 97 μm, 75 μm, 57 μm, 49 μm from top to bottom successively) obtain wanting micro-
Meter ruler cun single crystal grain.
(2) preparation of single crystal grain solaode:
1st, preparing a layer thickness in the glass substrate cleaning up using czochralski method is 35 μm of Radix Acaciae senegalis thin film.
2nd, weigh the cztsse single crystal grain 15g using molten-salt growth method preparation, sieved (each layer of test sieve using test sieve
Aperture is 97 μm from top to bottom successively, 75 μm, 57 μm, 49 μm), choose 75～97 μm of granule.
3rd, above-mentioned granule is evenly mixed in epoxy resin, single crystal grain is 1:2 with the volume ratio of epoxy resin, and plus
Enter the 1% of single crystal grain and epoxy resin quality summation polyacrylamide amine dispersant (or sodium lauryl sulphate, fatty acid
Macrogol ester), then, coating a layer thickness on Radix Acaciae senegalis thin film using cladding process is 125 μm be mixed with
The epoxy resin of cztsse single crystal grain.
4th, epoxy resin (or polyurethane adhesive, the silicon on 90 μm of top layer after epoxy resin cure, is ground away using grinder
Rubber), expose cztsse single crystal grain.
5th, clean up, using hcl and deionized water, the surface exposing cztsse single crystal grain, dry.
6th, thin film is sent into sputtering chamber, make in the mo thin film of 1.5 μm of surface sputtering sedimentation exposing cztsse single crystal grain
For dorsum electrode layer.
7th, take out sample, soak in deionized water and take thin film off after separating substrate and acacia gum layer, dry.
8th, the thin film taken off is laid on glass, is coated with the surface of mo layer down, send into plasma etching room, utilize
Plasma etching 15min, etches away Radix Acaciae senegalis and the epoxy resin of particle surface residual, exposes cztsse single crystal grain
Spherical surface.
The 9th, the cds cushion of 50nm is prepared using cbd method on cztsse single crystal grain spherical surface.
10th, the thin film being prepared for cds cushion is sent into sputtering chamber, preparation is successively sputtered on cds cushion and is about
The azo thin film of the i-zno layer of 150nm and 1 μm.
11st, take down support substrate, electrode evaporation, form complete no substrate flexibility cztsse single crystal grain solar-electricity
Pond.
The film preparation solaode of the mo/cztsse/cds/i-zno/azo structure that the present embodiment prepares, its
Open-circuit voltage voc=480mv, i=24ma, ff=56%, the conversion ratio of battery is 7.8%.
Embodiment 5
Experimental technique with embodiment 4, unique unlike cztsse single crystal grain preparation, comprise the following steps:
1st, hydro-thermal method preparation cu2znsns4Nano-particle: with embodiment 1.
2nd, 18 mmol cus, 12 mmol zns, 10 mmol sn, 6 mmol s, 4 mmol se, 50 mmol are weighed
Cscl, and it is fully ground so as to mix homogeneously after adding 1 mmol czts nano-particle mixing；Mixed after grinding uniformly
Close sample to load in quartzy bottle, reach 10～10 by three-way valve using vacuum pump assembly evacuation2Pa(can also use indifferent gas
Body is protected), thus excluding the impact that air reacts to fused salt, with oxyhydrogen flame by quartzy bottle closure；Equipped with aggregate sample after sealing
The quartzy bottle of product is placed in common heating furnace and is heated to 800 DEG C of holding 48h from room temperature, then cools to 600 DEG C about taking-up stones
English bottle fast cooling are to room temperature (putting in water)；Sample is taken out from quartzy bottle, fluxes through repeated ultrasonic washing removing
Agent cscl, sample is placed in 80 DEG C of drying 2 h of drying baker, obtains the granule that surface has crystal gloss.Finally by the sample of gained
Product are sieved the micron-scale that (test sieve each layer aperture is 97 μm, 75 μm, 57 μm, 49 μm from top to bottom successively) obtains wanting
Single crystal grain.
Comparative example 1
With embodiment 1, unique except for the difference that single crystal grain is 2:1 with the volume ratio of epoxy resin to experimental technique, result table
Bright: single crystal grain is excessive and epoxy resin is less, cause epoxy resin cannot by all of single crystal grain adhere to together it is impossible to
Prepare the single crystal grain thin film of good quality, and then linerless bottom flexible solar battery cannot be prepared.
With embodiment 4, unique except for the difference that single crystal grain is 1:5 with the volume ratio of epoxy resin to experimental technique, result table
Bright: single crystal grain is less and epoxy resin is excessive, leads to not prepare the compact arranged fexible film of single crystal grain, serious shadow
Ring the efficiency of prepared single crystal grain thin-film solar cells.
Comparative example 2
With embodiment 1, the addition of unique except for the difference that dispersant is that single crystal grain is mixed with epoxy resin to experimental technique
The 1/2000 of amount of substance summation, result shows: single crystal grain cannot dispersed in the epoxy, lead to not prepare list
The fexible film of brilliant even particle distribution, and then the linerless bottom flexible unitary particle film that single crystal grain is evenly distributed cannot be prepared
Solaode.
Comparative example 3
With embodiment 1, the thickness of unique except for the difference that Radix Acaciae senegalis is 100 μm to experimental technique, and result shows: in cleaning
During Radix Acaciae senegalis, the phenomenon coming off in a large number in single crystal grain, leads to not to prepare constitutionally stable single crystal grain thin
Film, further it is impossible to prepare linerless bottom flexible unitary particle film solaode.
Claims (9)
1. a kind of preparation method of single crystal grain thin film is it is characterised in that comprise the following steps:
S1. using czochralski method, one layer of Radix Acaciae senegalis thin film is prepared on substrate；
S2. choose 75～97 μm of single crystal grain, and mix with adhesive, add dispersant afterwards；Described single crystal grain and glue
The volume ratio of glutinous agent is 1:1.5～2, and the addition of described dispersant is single crystal grain and adhesive mixture quality summation
0.1～1%；
S3. the mixture of single crystal grain, adhesive and dispersant is coated on Radix Acaciae senegalis thin film, cured, grinding dew
After going out single crystal grain surface, cleaning-drying obtains final product single crystal grain thin film；
Adhesive described in s2 is selected from epoxy resin, polyurethane adhesive, silicone rubber；
Single crystal grain described in s2 is copper-zinc-tin-sulfur single crystal grain or copper zinc tin sulfur selenium single crystal grain；Wherein, described copper-zinc-tin-sulfur
The preparation method of single crystal grain is: (1) is by reaction raw materials elemental copper powder/cus powder, simple substance zinc powder/zns powder, simple substance
Tin powder/sns powder, simple substance sulfur powder or cus powder, zns powder, the mixing of sns powder, add flux, copper-zinc-tin-sulfur to receive
Rice grain ground and mixed is uniformly configured to presoma；In described reaction raw materials, copper, zinc, stannum, the mol ratio of four kinds of elements of sulfur are:
Cu/ (zn+sn)=0.76～0.95, zn/sn=1.1～1.2, (cu+zn+sn)/s=1；(2) presoma is loaded quartz reaction to hold
In device, evacuation or seal quartz reaction container using high temperature oxyhydrogen flame after being passed through noble gases；(3) will be anti-for the quartz after sealing
Answer container to keep 48～120h at 750～1000 DEG C, to quartz reaction container fast cooling to room temperature, take out quartz reaction and hold
Sample in device, obtains final product copper-zinc-tin-sulfur single crystal grain after washing, drying；
The preparation method of described copper zinc tin sulfur selenium single crystal grain is: (1) is by reaction raw materials elemental copper powder/cus powder, simple substance zinc
Powder/zns powder, simple substance tin powder/sns powder, simple substance sulfur powder, simple substance selenium powder or cus powder, zns powder, sns powder
End, the mixing of se powder, add flux, copper-zinc-tin-sulfur nano-particle ground and mixed to be uniformly configured to presoma；Described reaction is former
In material, copper, zinc, stannum, sulfur, the mol ratio of five kinds of elements of selenium are: cu/ (zn+sn)=0.76～0.95, zn/sn=1.1～1.2, (cu
+ zn+sn)/(s+se)=0.8～1, se/s=0.1～0.9；(2) presoma is loaded in quartz reaction container, evacuation or logical
Quartz reaction container is sealed after entering noble gases；(3) the quartz reaction container after sealing is kept 48 at 750～1000 DEG C～
120h, to quartz reaction container fast cooling to room temperature, takes out the sample in quartz reaction container, obtains final product copper after washing, drying
Zinc tin sulfur selenium single crystal grain；
The preparation method of described copper-zinc-tin-sulfur nano-particle is: (1) by zinc chloride, stannous chloride, copper chloride by 1:1:2 mole
Stir to obtain settled solution a than soluble in water；(2) solution b is the thiourea solution of 0.1～0.3m, the body of described solution a and solution b
Long-pending ratio is 2.5～3.5:1.5～2.5, solution b is added slowly in solution a under agitation, obtains turbid solution, afterwards again
Stir to obtain mixed solution；(3) mixed solution is placed in 170～190 DEG C of reaction 15～18h in autoclave, is cooled to room temperature
Obtain copper-zinc-tin-sulfur nano-particle by after washing, be centrifuged, being dried.
2. according to claim 1 the preparation method of single crystal grain thin film it is characterised in that the Radix Acaciae senegalis described in s1 are thin
The thickness of film is 20～40 μm.
3. according to claim 1 the preparation method of single crystal grain thin film it is characterised in that single crystal grain, gluing described in s3
The coating thickness of the mixture of agent and dispersant is 110～130 μm.
4. according to claim 1 single crystal grain thin film preparation method it is characterised in that the grinding described in s3 refer to grind
Fall Radix Acaciae senegalis thin film and adhesive, the thickness of grinding is 70～90 μm.
5. according to claim 1 single crystal grain thin film preparation method it is characterised in that dispersant described in s2 be selected from poly- third
Acrylamide, sodium lauryl sulphate, fatty acid polyethylene glycol ester.
6. the single crystal grain thin film that any one of claim 1 to 5 methods described prepares.
7. a kind of linerless bottom flexible unitary particle film solaode is it is characterised in that contain monocrystalline described in claim 6
Grain thin film.
8. a kind of method preparing single crystal grain thin-film solar cells described in claim 7 is it is characterised in that include following walking
Rapid:
S1. using the molybdenum film of 1～2 μm of single crystal grain film surface sputtering sedimentation as dorsum electrode layer；
S2. take out sample, separate single crystal grain thin film and dry, single crystal grain thin film is laid in hard substrates, is coated with molybdenum
The surface of thin film down, etches away Radix Acaciae senegalis and the adhesive of single crystal grain remained on surface；
S3., cds cushion, Window layer i-zno and transparent electrode layer azo, evaporation electricity are sequentially prepared on single crystal grain thin film
Pole, encapsulation, obtain final product linerless bottom flexible unitary granule solaode.
9. prepare the method for the solaode of single crystal grain thin film according to claim 8 it is characterised in that described cds
The thickness of cushion is 40～60nm；The thickness of described Window layer i-zno and transparent electrode layer azo be respectively 100～400nm and
0.4～1 μm.
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| CN108342776B (en) * | 2018-02-12 | 2020-01-03 | 岭南师范学院 | Copper-zinc-tin-sulfur single crystal particle film and photoelectrochemistry full decomposition pure water device |
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